The present invention relates to applied ultraviolet (UV) Raman spectroscopy and chemical detection and identification. More specifically, the present invention relates to devices, systems and methods for remotely detecting hazardous substances that may be on a surface.
In the field of chemical sensing or detecting, it is desirable to quickly detect substances at a contaminated scene and report information about the substances types and locations in order to prevent others from coming into contact or influence with the detected substance. It is also a key factor in improving consequence management by providing the decision makers with the information needed to scale and direct the response effort.
Spectroscopy techniques are used to analyze substances and techniques have been developed for the non-destructive testing of surface-deposited substances in solid and liquid phases. Such techniques include Fourier Transform Infrared Spectroscopy (FTIR), X-ray fluorescence, gas chromatography and mass spectrometry (GC-MS), and Infrared Raman spectroscopy (IR Raman). Currently available surface-hazard detectors are “point-and-shoot” devices, in which the device operator holds a sensing probe on a specific location at very close range and dwells on that specific location for an amount of time to provide sufficient integration time in the detector or, in the case of GC-MS, to intake enough surface compounds in vapor phase to carry out the analysis. Thus, these devices require the operator to approach very close to a potentially harmful substance and maintain proximity to that substance long enough to obtain a single measurement. The task of surveying a large area or region for potentially harmful substances is therefore daunting and requires judicious sampling strategies to maximize the efficiency of the process. The most challenging aspect associated with searching contaminants dispersed on a surface resides in the variety of chemical species a sensor is exposed to during a search.
Surface contamination can be the result of an accident or intentional dispersion of the contaminant, and therefore the surface contamination can consist of a single chemical or multiple chemicals in bulk form or dispersed over a wide area. In the case of persistent patches of contamination composed of thin layers, small droplets or small particles, none of the above mentioned methods provide adequate detection capabilities.
For example, a commercially available FTIR system for emergency response requires 20 seconds to carry out a single sample-identification analysis, while the sample needs to be physically removed from the surface and presented to the sensor. Another example is a commercially available IR-Raman system for emergency response that requires a maximum distance of 15 mm and measurement times typically between 1 and 5 seconds with up to 20 seconds for some samples.
UV Raman spectroscopy has many unique properties that can be advantageously employed in the rapid standoff detection and identification of surface-deposited hazards. The high degree of information content inherent in Raman spectroscopy provides the ability to differentiate structurally similar chemicals with low false alarm rates. The information content is associated with the vibrational degrees of freedom associated with any molecule. This wealth of vibrational modes manifests itself in rich, narrow Raman peaks that provide a spectral fingerprint for a given Raman active material. Spontaneous Raman scattering, however, has an intrinsically weak cross-section. The intensity and quality of the Raman spectrum depends on (1) the wavelength, linewidth and spectral purity of the excitation light, (2) the extent to which the excitation or scattered light is absorbed, the amount of interfering fluorescence that is emitted, and the potential existence of interfering laser-induced breakdown emission of surface materials, (3) the thermal and photochemical stability of the sample under excitation, and (4) the number or chemicals simultaneously interrogated (spectral congestion). Therefore to maximize usability in practical applications, UV Raman sensors capitalize on a short wavelength resulting in larger scattering cross-sections, a reduced natural fluorescence background (no photo-bleaching required), a solar-blind spectral region below 300 nm (important for a standoff sensor) and resonance enhancement of the Raman scattering cross-section for some vibrational transitions. In addition, UV light sources below 300-nm present virtually no eye hazard to personnel wearing standard plastic or non-crystalline glass eye-protection.
A surface-hazard detection system is needed that can safely interrogate surfaces from greater distances and that can do it with a high degree of flexibility in the adjustment of the sensor field of interest. This standoff surface-hazard detection system needs also to rapidly analyze returned optical radiation from the substance in order to provide the high data throughput that enables large perimeter searches. UV Raman spectroscopy provides the foundation for this high performance sensor.